ES2362460T3 - MIXED CRYSTALS, PROCEDURE FOR OBTAINING AND USE IN THE MANUFACTURE OF BAKERY PRODUCTS. - Google Patents

Abstract

Mixed crystals comprise 100 ppmw of leavening agents and 0.1-5000 ppmw of crystallization additive. A polymer is crystallized by using the crystallization additive. The polymer is hydrophilic cellulose derivatives. An independent claim is also included for a method for preparing the mixed crystals, which involves adding crystallization additive and leavening agent during crystallization of polymer.

Description

The present invention comprises mixed crystals containing a) leavening agent and b) 0.1 to 5000 ppm by weight of anti-caking agents, in relation to the total amount of the leavening agent, in the form of at least one polymer, in which when using derivatives Hydrophilic cellulose as anti-caking agents its amount is reduced to less than 100 ppm by weight, in relation to the total amount of the leavening agent. Likewise, the present invention comprises obtaining mixed crystals and their use in obtaining bakery products, as a regulator of acidity in foods, in obtaining cosmetic products, in the synthesis and formulation of pharmaceutical products and as an agent of expansion in technical procedures, for example, of foam rubber or for firefighting formulations. In addition, the present invention comprises the manufacture of bakery products.

For the manufacture of porous bakery products, before and / or during the baking process, in the dough a gas is generated or said dough is mixed with gas, to produce the porosity in the finished baked product thanks to the gas bubbles. In the simplest case, before baking the dough is mixed with a gas, generally, air, for example, through the intense shaking of the dough or one of its components before mixing. The best known mode of execution is the addition to the whipped egg white dough. It is also possible to incorporate in the dough a gas, for example, air, through nozzles. The processes in which water vapor loosen the dough are also known, for example, in the case of obtaining puff pastry. The most commonly used gas is, however, carbon dioxide or carbon dioxide mixed with ammonia and water vapor. Carbon dioxide is generated, for example, in biological form, during the process of fermenting components of the dough through yeasts (yeast dough) and / or lactic acid bacteria (in the so-called recentadura). Alternatively or additionally to the use of yeast or recentature, carbon dioxide is also generated, or a mixture of carbon dioxide, ammonia and water vapor, also obtained chemically thanks to baking aids, the so-called leavening agents or, colloquially , "leavening powder", which are added to the dough.

Leaving agents generally contain at least one carbonate and, in case the temperature increase is not sufficient to disintegrate, an acidic or acidifying substance. In addition to carbonate, they also contain, optionally, carbamate (old name: "carbonate"). The carbonate and / or carbamate is selected according to the corresponding baked product, for example, for spice or honey bread, potassium carbonate is often used, for Cenceño bakery products, sodium hydrogen carbonate (old name: "bicarbonate sodium "), ammonium hydrogen carbonate (" ammonium bicarbonate ", abbreviated" ABC "), as the sole carbonate or mixed with ammonium carbamate (" ammonium carbonate "). The acid or acidifier should not, even together with the carbonate or carbamate residues that volatilize, negatively influence the taste. Compounds such as dextrotartaric acid or its salts are usually used, for example, potassium, sodium, potassium and / or calcium tartar, citronic acid, calcium hydrogen phosphate, sodium hydrogen pyrophosphate or sodium and aluminum phosphate. If the leavening agent contains an acid or acidifier, in general a separator is added that prevents the premature formation of carbon dioxide through the reaction of the carbonate with the acid or the acidifier, usually flour or starch is added thereto. The ammonium compounds mentioned ABC and ammonia carbonate already disintegrate through the temperature increase to at least 60 ° C without leaving any residue and form carbon dioxide, ammonium and water. In the case of typical baking temperatures, the three components are obtained in the form of gas and therefore all contribute to an increase in the porosity of the baked product. Therefore, these compounds are usually used without the addition of an acid or acidifier, so that the addition of a separator is not necessary.

In the Ullmanns Encyklopädie der technischen Chemie (Encyclopedia of Technical Chemistry Ullmann), 3rd edition, Urban & Schwarzenhäuser, Munich - Berlin 1953, entry: "Backpulver" (baking powder) or in Ullmann’s

6th

Encyclopedia of Industrial Chemistry, edition, 1999 electronic version, Wiley-VCH, Weinheim 1999, entry "Bread and other baked Products", point 2.6: "Leavening Agents" (agents leudantes), provide an overview of the known procedures for obtaining porous bakery products using leavening agents. Obtaining ammonium compounds such as carbonate, bicarbonate and ammonium carbonate through the conversion of amounts of ammonia and carbon dioxide corresponding to the desired product, in aqueous mother liquor, with the pressure and temperature conditions according to the product, followed by the separation and drying of precipitation, has also been known for some time and is described in the Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, 1999 electronic version, Wiley-VCH, Weinheim 1999, entry: "Ammonium Compounds "(Ammonium compounds), above all, item 4 .:" Ammonium Carbonates "(ammonium carbonates. The production of alkali hydrogen carbonates and carbonates is also known.

Although in the case of usual baking temperatures these ammonium compounds are obtained in gaseous form, an anti-caking agent is often added, to avoid agglomerate, in English "caking", the generation of lumps or larger agglomerates in a powder (in German the term anti-caking agent has the same etymology as baked, but this does not mean that it is therefore linked to the procedure). As anti-caking agent they are used

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usually, cornmeal, magnesium oxide or magnesium carbonate in an amount of 2000 to 10,000 ppm by weight. Eventually, inorganic salts are also mixed with the anti-caking agents.

EP-A 1 161 872 publishes the implementation of anti-caking agents based on hydrophilic cellulose derivatives. Sodium carboxymethyl cellulose is mentioned as the preferred hydrophilic cellulose derivatives. It is mentioned that the cellulose derivative is used in an amount of at least 100 ppm by weight, in relation to the total amount of leavening agent, especially preferably at least 500 ppm by weight, for example 1000 ppm by weight

US-A 3 930 032 publishes a stable modified leavening agent, because sodium carbonate is coated with cellulose derivatives. This coated leavening agent contains 3% cellulose derivatives.

Hydrophilic cellulose derivatives are used in bakery products not only as anti-caking agents, but also as fillers in an amount of, usually, 5 to 20% by weight in relation to the bakery product (US 4 678 672 and GB 745 926). Likewise, the use of carboxymethyl cellulose as a thickener in the usual amount of 0.5 to 1% by weight in relation to the bakery product (EP-A 399 995) is known.

The implementation of anti-caking agents is also widely disseminated in fertilizers, since fertilizers must have a comparatively stable storage because their use is only done seasonally.

As anti-caking agents, for example, glues based on carboxymethyl cellulose, mixed with filler material, such as calcium carbonate or calcium oxide (DD-A 117 787), synthetic polymers, for example carboxymethyl cellulose or methyl cellulose and a surface of surface action (US 3 388 990 / US 5 472 476), hydroxypropylcellulose, sodium carboxymethylcellulose or hydroxypropylmethylcellulose (EP-A 246 719) or sodium carboxymethylcellulose and a surface acting substance (SU-A 1570255).

In the current state of the art, a coating with a protective film for inorganic salts is also published. The protective film describes, for example, polysaccharides and their derivatives, especially starch, cellulose, manna, sodium alginate, methyl cellulose, carboxymethyl starch and carboxymethyl cellulose (DE-A 28 21 703, WO 98/56595). Likewise, water-soluble cellulose esters (EP-A 461 886) or polymers that form films, such as methylcellulose, hydroxybutylmethylcellulose, sodium carbosimethylcellulose, hydroxyethylmethylcellulose or hydroxypropylmethylcellulose (DE-A 24 35 008), are used for coating the particles. . Eventually, other anti-caking agents can be used, such as magnesium silicate (WO 94/24860, WO 94/24994, US 5 482 702)

or phosphorus compounds (US 5 468 716).

The disadvantage of the current state of the art is that in the case of the known baking process, using usual leavening agents, the formation of large gas bubbles and, as a consequence, hollow spaces of undesired magnitudes in the baked material cannot be completely prevented , despite the use of anti-caking agents. These large hollow spaces usually far exceed the desired pore diameter of 0.1-approx. 5 mm of the pores in the baked material. This produces a high proportion of waste, since said baked material contains large isolated hollow spaces but otherwise, areas with a reduced undesirable porosity, which makes it hard and often unpleasant in appearance. If large hollow spaces arise on the surface of the material, during the baking process the thin layer of surface dough will cook faster and will have an unpleasant dark brown or black coloration. These products cannot be sold and increase production waste.

The agglomerate of the usual leavening agents has its origin, among others, in the crystalline form of the products. The technically available salts have a very rough structure due to epitaxy and other crystal defects. These crystalline forms can be easily hooked due to said rough structure and form mechanically stable bridges between the individual crystals. Stable bridges cause a known tendency to mass agglomerations of products. Figure 1 shows an agglomerate of ammonium bicarbonate, usually used in the current state of the art as a leavening agent.

In the current state of the art, anti-caking agents are then used in the leavening agent, to reduce the engagement and, thereby, the agglomeration of the crystals of the leavening agents. The anti-caking agent is therefore used as a separator or for coating / coating the rough crystalline structure (EP-A 1 161 872), to soften it.

In addition, said mixture of leavening agent and anti-caking agent has disadvantages in the continuous process of manufacturing bakery products (automated production line). Usually, such mixtures are incorporated into powder through a dosing device. To avoid agglomeration of the mixture in the dosing device, it is constantly stirred. But this movement unfortunately causes a separation of the leavening agent and the anti-caking agent. As a consequence, the anti-caking agent is no longer found

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distributed regularly in the leavening agent and agglomerations can occur and, with it, the unwanted formation of hollow spaces of irregular sizes in the product and, as a consequence, a greater amount of waste.

Another disadvantage of the leavening agent of the current state of the art is its reduced storage stability. Especially in the case of the usual application area of storage under pressure in the current state of the art and after a few days agglomerations can be verified both in the coated leaving agents as well as in the pure powder mixture of leavening and anti-caking agent. Storage under pressure is very common, since due to lack of space the bags are stored on top of each other.

As a consequence, despite the use of anti-caking agents, agglomerations, that is, the generation of lumps or other larger agglomerations are still an unsolved problem in the storage and use of leavening agents. The agglomerations cause the formation of hollow spaces of undesired magnitudes and, with it, an irregular distribution of hollow spaces.

The object of the present invention is, therefore, to present a modified leavening agent which, in comparison with the current state of the art, is less agglomerated and / or whose agglomerates can be easily released again. Likewise, it is first desired to modify the cause of the agglomeration in the first place and in comparison with the current state of the art, that is, of the crystalline form of the leavening agent, instead of minimizing only the effect of the crystalline form. In addition, said modified leavening agent must still be able to form a sliding powder after prolonged storage, despite the use of a very small amount of adjuvant, which can be accurately dosed in the application in automated / continuous baking lines. Especially in obtaining bakery products it is desired to avoid the presence of hollow spaces of undesired magnitudes.

Surprisingly, it was discovered that mixed crystals containing

a) leavening agents

b) 0.1 to 5000 ppm by weight of crystallization aids, in relation to the total amount of the leavening agent, in the form of at least one polymer, where mixtures of different polymers can also be used, where in the If the hydrophilic cellulose derivatives are used as crystallization aids, their quantity is reduced to less than 100 ppm by weight, in relation to the total amount of the leavening agent, they have a regular non-agglomerated crystalline structure.

By the term mixed crystals it is understood, in the present invention, that the crystallization aids (component b) are found within and / or on the glass of the leavening agent (component a), that is, on the crystal and / or on or in contact with the surface of the glass.

The mixed crystals therefore represent a modified leavening agent.

By "sliding" it is understood in the present invention that after storage or transport in bags the product is not in the form of solid pieces, that is, many lumps have been formed, but rather drained.

By "lump free" it is understood in the present invention that the sliding powder is free of agglomerates formed during storage.

The mixed crystals according to the invention have a uniform, rounded and smooth crystalline structure and thus not agglomerated (see Figures 3 A / B, 4 A / B and 5).

Significantly less agglomerates are formed during storage and use which, moreover, can be released more easily than those of the leavening agents of the current state of the art.

The leavening agent (component a) contains at least one carbonate. As carbonate, those whose use is harmless in food and which, like their decomposition products, do not cause an unpleasant taste in finished bakery products are selected. Suitable carbonates, contained individually or in mixtures, are known to the specialist and usually alkali carbonates and hydrogen carbonates are used, especially sodium carbonate, sodium hydrogen carbonate, potassium carbonate and carbonate carbonate. potassium hydrogen as well as ammonium carbonate and ammonium hydrogen carbonate.

Equally suitable is the mixture known as "deer antler salt" of ammonium carbonate and ammonium hydrogen carbonate, which may additionally contain ammonium carbamate.

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Preferably, the carbonate is ammonium hydrogen carbonate and / or ammonium carbonate. Especially preferred, the carbonate is ammonium hydrogen carbonate (also called ammonium bicarbonate).

The average particle diameter of the carbonates used is generally 50 to 1000 µm, preferably 75 to 700 µm, preferably 150 to 500 µm.

Optionally, the leavening agent additionally contains one or multiple carbamates. As carbamate, those whose use is harmless in food and which, like their decomposition products, do not cause an unpleasant taste in finished bakery products are selected. A suitable carbamate is, for example, ammonium carbamate.

In the case that the leavening agent contains carbamate, the amount of carbamate is preferably from 10 to 90% by weight, in relation to the total amount of the leavening agent, preferably, from 30 to 70% by weight, especially, approximately 50% by weight. The mixture in equal parts of ammonium carbamate and ammonium bicarbonate is also called ammonium carbonate.

If the leavening agent used contains components that do not decompose, or do not do so sufficiently when heated to usual baking temperatures of, for example, 100 to 200 ° C, the leavening agent additionally contains an acid or an acidifier. The acid or acidifier is a compound or a mixture of compounds, known for these purposes, for example, potassium, sodium, potassium and / or calcium tartar, citronic acid, calcium hydrogen phosphate, sodium hydrogen pyrophosphate and / or sodium phosphate and aluminum. In the case that the leavening agent contains acids or acidifiers, its amount is preferably of an amount necessary for the conversion of the leavening agent and, thereby, for the release of carbon dioxide. Depending on the intensity of the acid, the amount of protons per molecule and the molar weight of the acid and the leavening agent, this amount can vary considerably. As an example, an amount of 60 to 250% by weight is used in the use of sodium bicarbonate and for usual acid carriers, in relation to the total amount of leavening agent, preferably 75 to 225% by weight.

If the leavening agent contains an acid or acidifier, a separator is preferably added that prevents the premature formation of carbon dioxide through the reaction of the carbonate with the acid or the acidifier. Said separators are known, preferably, they are flour and / or starch.

The average particle diameter of the acids or acidifiers used is generally 50 to 1000 µm, preferably 75 to 700 µm, preferably 150 to 500 µm.

The carbonates, carbamates, acids or acidifiers mentioned, as well as the separators, can be purchased in the market.

The crystallization aids (component b) preferably contain at least one polymer that influences the crystallization. By "influencing crystallization" is understood, in the present invention, that the aggregate polymer suitably influences the crystalline form of the crystals obtained. Under the effect of polymers that influence crystallization, the crystals have a smooth and regular structure. Said structure is different from the crystalline structure without a polymer that influences crystallization, characterized by an irregular and rough surface due to epitaxy and other crystalline forms that produce a negative effect.

In addition, the polymer is preferably hydrophilic. Uncharged, anionic and / or cationic polymers that influence crystallization can be used.

In addition to the individual polymers, mixtures of the different non-charged, anionic and / or cationic polymers can be used. Uncharged polymers can also be used as components of the mixture of anionic and / or cationic polymers.

Said polymers are advantageously selected and for obvious reasons so that the polymer itself, as well as thermal disintegration products, are suitable, in the usual amounts, as food additives, without influencing the taste of bakery products. . Preferably, polymers of natural origin or those obtained through the modification of natural polymers, of neutral flavor, and authorized for use in food are used.

Naturally charged polymers are hydrophilic polymers based on sugar derivatives and / or peptides, especially from the (hetero) polysaccharide and / or (poly) peptide sectors.

These heteropolysaccharides are usually obtained through fermentation or isolation from natural sources.

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Especially preferred are (hetero) polysaccharides loaded with carboxyl or sulfonate side chains, especially with unmodified carboxyl groups (eg, pectin and / or alginate) and with modified carboxyl groups (eg, amidated pectin).

Advantageous anionic polymers are, for example, polyacrylic acids and their salts with ammonium, sodium or potassium, polymethacrylic acids and their salts with ammonium, sodium or potassium, acrylic acid and its salts with ammonium, sodium

or potassium, copolymers of methacrylic acid and its salts with ammonium, sodium or potassium, copolymers of acrylic acid and maleic acid and its salts with ammonium, sodium or potassium.

The mentioned anionic polymers may also contain vinyl sulfonic acid in different proportions.

All the mentioned anionic polymers can have partially esterified groups, where both aliphatic components and also derivatized on the basis of closed terminal group polyalkylene glycols can be used as an alcohol component. For the production of polyalkylene glycols, both ethylene oxide and propylene oxide and larger alkylene oxides can be used, alone in the form of random or block copolymers.

In addition, polyasparaginic acid and its salts with mono and divalent cations are preferred. Especially preferred salts are those of polyasparaginic acid with ammonium, sodium and potassium.

Advantageous cationic polymers are, for example, polyimines, polyvinylamines and copolymers with polyvinyl alcohol and / or poly dimethyl allyl ammonium chloride.

Non-ionic polymers are, for example, polyethylene glycols, polypropylene glycols, random and block polymers based on ethylene oxide with alkylene oxides, especially, propylene oxide and / or butylene oxide. Eventually, they also have an additional terminal group closure on one or both sides, with aliphatic terminal groups. In addition, polyvinylpyrrolidone and / or polyvinylpolypyrrolidone is preferred.

Especially preferred are those polymers that already have an authorization as a food component, for example: alginic acid (E 400), sodium alginate (E 401), potassium alginate (E 402), ammonia alginate (E 403) , calcium alginate (E 404), propylene glycol alginate (E 405), agar-agar (E 406), carrageenan (E 407), processed Eucheuma algae (E 407a), carob seed meal (E 410), flour of guar seeds (E 412), traganto (E 413), gum arabic (E414), xanthan (E 415), karaya (E 416), tara seed flour (E 417), gelane (E 418), glucomannan rubber komjac / konjac (E 425), soy bean polysaccharide (E426), pectin / amidated pectin (E 440), microcrystalline cellulose / cellulose powder (E 460), methyl cellulose (E 461), ethyl cellulose (E 462) , hydroxypropylcellulose (E 463), hydroxypropylmethylcellulose (E 464), ethylmethylcellulose (E 465), sodium carboxymethylcellulose / carboxymethylcellulose (E 466), cross-linked sodium carboxymethylcellulose (E 468), c enzymatic hydrolysis arboxymethylcellulose (E 469), polydextrose (E 1200), polyvinylpyrrolidone (E 1201), polyvinylpolypyrrolidone (E 1202), polished (E 1204), oxidized starch (E 1404), monoalmidon phosphate (E 1410), dialmidon (E 1412), phosphate dialmidon phosphate (E 1413), acetylated dialmidon phosphate (E 1414), acetylated starch (E 1420), acetylated dialmidon adipate (E 1422), hydroxypropyl starch (E 1440), hydroxypropyl starch phosphate ( E 1442), sodium octenyl succinate starch (E 1450), oxidized acetylated starch (E 1451).

Especially preferred are the crystallization aids selected from the group consisting of alginic acid (E 400), sodium alginate (E 401), potassium alginate (E 402), ammonia alginate (E 403), calcium alginate (E 404 ), propylene glycol alginate (E 405), pectin (E 440), amidated pectin (E 440), carrageenan (E 407), gelane (E418), gum arabic (E414), karaya (E 416), traganto (E 413) ) and / or xanthan (E 415), especially preferably, pectin (E 440) and / or amidated pectin (E 440).

In addition, linear and / or branched chain (poly) peptides are preferred as crystallization aids. Especially preferred, in the field of (poly) peptides, the qualities of gelatin.

Suitable cellulose derivatives are, for example, cellulose ethers. These are cellulose derivatives, which are formally obtained through the substitution of hydrogen atoms in the hydroxy groups of the cellulose through alkyl and / or arylalkyl groups, wherein said alkyl and / or arylalkyl groups can be substituted by nonionic, anionic and / or cationic functional groups. The alkyl groups are usually C1-C8 alkyl groups, which can be straight chain or branched chain. Preferably, the alkyl group is a C1C4 alkyl group, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, iso-butyl or tert-butyl. The alkyl group may be substituted by an aromatic radical to obtain an arylalkyl group, for example, with a phenyl radical. A preferred arylalkyl group is benzyl. The alkyl or arylalkyl group may be functionally substituted, for example, with hydroxy, carboxy or carboxylate groups. In the case that it contains a carboxylate group, the corresponding counterions are also contained, for example, alkali ions, such as sodium or potassium or ammonium ions. If it is only "carboxymethyl cellulose" (often abbreviated as "CMC"), it usually refers to

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sodium carboxymethylcellulose (also abbreviated, if necessary, as "Na-CMC"). Mixed alkyl ethers containing more than one type of alkyl-arylalkyl or functionally substituted alkyl group can also be used.

Preferred polymer hydrophilic cellulose derivatives are methyl, ethyl, propyl, carboxymethyl, hydroxyethyl, hydroxypropyl, methylhydroxidethyl, methylhydroxypropyl, methylhydroxybutyl, ethylhydroxidethyl, carboxymethylhydroxyethyl and / or benzylcellulose. Sodium compounds are preferred among carboxymethyl celluloses. The leavening agent preferably contains sodium carboxymethyl cellulose.

Cellulose ethers are obtained in a known manner, usually, through the effect of alkyl or aralkyl halides, epoxides or activated olefins on base activated cellulose (for example, caustic soda). Cellulose ethers are usual commercial products, also usually used in foods as thickeners. Cellulose ethers can be purchased, for example, with the "Tylose" brand, the high purity cellulose ether, for food applications, with the "Tylopur" brand, and the high-purity Na-CMC, with the brand "Tylopur C" by Clariant GmbH.

As counterions, in addition to hydrogen, alkali and / or alkaline earth ions, as well as substituted or unsubstituted amines, for example, ammonia, can also be used.

The obtaining of the mentioned polymers is known and can be consulted in the specialized literature.

The mixed crystals contain the crystallization aids preferably in an amount of 0.5 to 5000 ppm by weight, relative to the leavening agent, preferably 0.5 to 2000 ppm by weight, particularly preferably 1 to 1000 ppm. by weight, especially from 1 to 500 ppm by weight, especially preferably, especially from 1 to 100 ppm by weight, preferably, in addition, from 1 to 50 ppm by weight, even more preferably, from 1 to 20 ppm in weigh.

In the event that hydrophilic cellulose derivatives are used as crystallization aids, the amount of hydrophilic cellulose derivatives in the leavening agent is preferably less than 80 ppm by weight, relative to the leavening agent, preferably, between 0.5 and 50 ppm by weight, especially between 1 and 20 ppm by weight.

The increase in the amount of crystallization aids beyond a maximum value generates a negative influence on the modification of the crystal and the tendency to crystallization. In the case of the use of hydrophilic cellulose derivatives as crystallization aids and from a value of approximately 100 ppm by weight undesired configurations of columnar crystals are obtained instead of spherical crystals (see Figure 4 C).

Said columnar crystals tend, in turn, to become hooked and, thus, to agglomeration, similar to what occurs with ammonium bicarbonate of the current state of the art (see Figure 1). In addition, after some time they get wet and form a sticky dough. If more than 5000 ppm by weight of crystallization aids are used, predominantly large crystals and / or crystals with rough surfaces are obtained. Large crystals must then be ground before use. Grinding would mean a costly additional procedure step, which also brings with it the danger of the formation of rough surface particles.

Likewise, the present invention comprises the process for obtaining mixed crystals according to the invention characterized in that the crystallization aid is added before and / or during the crystallization step of the leavening agent.

It is preferred that the crystallization aid be added to the mother liquor from which the leavening agent crystallizes. In this case, the crystallization aid is added to the mother liquor usually moved in circles, in which the carbonate and, eventually, the hydrogen carbonate are obtained and crystallized.

The procedure for obtaining the leavening agent has long been known to the specialist. For example, ammonium compounds, such as carbonate, bicarbonate and ammonium carbonate, are obtained through the conversion of amounts of ammonia and carbon dioxide corresponding to the desired product, usually 10 to 20%, and carbon dioxide added in excess. , usually, 30 to 65% in the aqueous mother liquor, with the conditions of pressure usually, 1 to 6 bar and of temperature, usually, 30 to 65 ° C followed by the separation and drying of the precipitations

The detailed description of obtaining a leavening agent can be found in the Ullmann’s Encyclopedia of Industrial Chemistry (Ullmann Encyclopedia of Industrial Chemistry), 2008 edition.

The dosage amount of crystallization aids in the mother liquor corresponds, in the case of a continuous process after a concentration phase, to the amount of mixed components present in the separated crystals.

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After obtaining the mixed crystals according to the invention, other auxiliary substances can optionally be added thereto; for example, known anti-caking agents, such as cornmeal, magnesium oxide and / or magnesium carbonate or known separators, such as fatty acid salts, for example, stearic acid, calcium and / or magnesium stearate, silicates, silicon dioxide , talc or other usual anti-caking agents. However, one of the advantages of the process according to the invention is that it is possible to reduce the quantity or dispense completely with said additives. Dosages of more than 5000 ppm of magnesium carbonate are only suitable in the case of extreme temperatures and storage times.

In addition, the present invention comprises the use of mixed crystals for the production of bakery products, as a regulator of acidity in foods, in the obtaining of cosmetic products, in the synthesis and formulation of pharmaceutical products and as an expanding agent in procedures. technicians, for example, of foam rubber or for fire extinguishing formulations.

The present invention also comprises a process for obtaining bakery products, characterized in that the mixed crystals according to the invention are used as a modified leavening agent.

Otherwise, the procedure for obtaining bakery products is carried out in a manner known to the specialist.

The process for obtaining bakery products is further characterized in that a dough is prepared that usually contains a source of starch, such as flour and / or potato starch, a source of protein, such as egg white, often fat, such as butter, oil and / or margarine, and generally other ingredients such as sugar, spices, fruits or the like. The ingredients are mixed mechanically, as usual, for example, by mixing or kneading. In addition to the leavening agent, other ingredients that also contribute to the porosity of bakery products can be used, for example, yeasts and / or recentature, likewise, the porosity can be increased through the insufflation of gases, such as air, in the mass. The leavening agent can also be pre-mixed with individual components before preparing the dough itself. In addition, it can be mixed with dry components of the dough, for example, flour, sugar, spices, other additives and / or dried eggs to prepare a baking mixture with which, by adding liquid, you get the dough that will then be baked .

The amount of added leavening agent, with modified crystalline form, is selected so that the desired porosity is regulated, this can be optimized by a few routine tests.

Usually, the amount of leavening agent is selected so that for every 100 g of starch source (for example, flour and / or potato starch), 1.5 to 3.5 g of gases (dioxide) are advantageously obtained carbon, ammonia and / or water vapor), preferably 2 to 3 g of gases, especially 2.35 to 2.85 g of gases.

If non-porous bakery products are manufactured, the quantity should be reduced accordingly; for porous products it is increased.

The advantage of the present invention is that the mixed crystals according to the invention have a rounded shape and a smooth surface. Thus, during storage and use of the mixed crystals according to the invention as a modified leavening agent, noticeably less agglomerates are formed which, moreover, can be easily released again.

Since the crystallization aids are present, together with the leavening agent in a mixed crystal, it is also avoided that an unwanted separation is caused.

In addition, the object of avoiding agglomerations has already been achieved with a very small amount of crystallization aids. Also, an additional procedural step is no longer necessary to obtain the leavening agent.

Bakery products are obtained with a porosity that can be controlled very well.

Examples

1. Crystallization

Ammonium bicarbonate (ABC), water and additives are heated to 40 ° C, according to table 1 under stirring. After complete dissolution it is rapidly cooled to 0 ° C, with stirring. The crystals obtained are refrigerated, dried and analyzed under a microscope with an increase of 20: 1.

Table 1:

Witness test

ABC [g]

water [g] additive

1. (comparison sample)

30.8 131.2 0 figure 2

Pectin

ABC [g]

water [g] additive [mg]

2.

30.8 131.2 0.31 (10 ppm) figure 3 A

3.

30.8 131.2 1.5 (50 ppm) figure 3 B

Tylose

ABC [g]

water [g] additive [mg]

Four.

30.8 131.2 0.15 (5 ppm) figure 4 A

5.

30.8 131.2 0.75 (25 ppm) figure 4B

6. (comparison test, analogous to EP 1 161 872)

30.8 131.2 31 (1000 ppm) figure 4 C

Jelly

ABC [g]

water [g] additive [mg]

7.

30.8 131.2 0.31 (10 ppm) figure 5

The results are represented in figures 2 to 5.

The agglomeration tendency of the ammonium bicarbonate crystals 5 can be clearly seen in Figures 2 and 4C. The mixed crystals according to the invention (Figures 3 A / B, 4 A / B and 5), on the other hand, only have isolated crystals with the same magnification, which also have no tendency to agglomerate.

2. Penetration test

Sample 1: mixed crystals of ABC and 2 ppm of pectin, 3000 ppm of magnesium carbonate as anti-caking agent Sample 2 ABC without addition of crystallization aids (current state of the art), 3000 ppm of magnesium carbonate 10 as anti-caking agent.

Both samples were stored 2 weeks under a pressure of 1.25 kPa. Subsequently, the penetromer was placed in the center of the stored product and a greater weight was applied. The thickness of the layer was 15 mm. The results are summarized in Table 2 and can be seen in Figure 6.

Table 2:

Cone Weight [g]

sample 1 insertion depth [mm] sample 2 insertion depth [mm]

0

0

0

170

3 one

350

5 one

531

10 3

713

12 3

896

fifteen 3

1081

3

1267

5

1454

5

1642

5

1831

5

2021

5

2206

5

2391

5

2579

5

While in sample 2 the cone only penetrated step by step (the plateaus are represented in the weight curve of the insertion depth) and also in the case of a greater weight load it did not penetrate deeply into the product, in the case of sample 1 the cone penetrated the product practically proportional to the

5 increase in weight, until the product moved completely.

From the results of table 2 it follows that the mixed crystals according to the invention (sample 1) in comparison with the current state of the art (sample 2) are very sliding and do not even have in part agglomerations when subjected to Pressure. The sample corresponding to the current state of the art (sample 2), however, already exerts a light pressure and presents agglomerations.

10 3. Post storage storage For the storage test, 25 kg plastic bags were filled with fresh produce and weights were placed

on top (pallets with storage material). The bags were subsequently opened and the material analyzed. The storage conditions are gathered in tables 3.1 to 3.3. The degree of agglomeration of ammonium bicarbonate (ABC) was rated on a scale of 1 to 5.

15 Evaluation: 1 = ABC is free of lumps and is very sliding 2 = ABC can be easily loosened, after which it is very sliding; there are no lumps 3 = ABC can be easily loosened, after which it is very sliding; small lumps remain 4 = ABC cannot be easily loosened, after which it is little sliding; large lumps remain

20 5 = ABC cannot be loosened / not sliding To all the samples in the following table, the indicated amount of magnesium carbonate as an anti-caking agent was added additionally after crystallization.

Table 3.1:

ABC according to the current state of the art, 500 ppm of MgCO3

mixed crystals of ABC and 2 ppm of pectin, 500 ppm of MgCO3

Load: 1 ton Storage: 1 month

(figure 7 A) (figure 7 B)

Evaluation:

4 one

Table 3.2:

ABC according to the current state of the art, 3000 ppm of MgCO3

mixed crystals of ABC and 2 ppm of pectin, 3000 ppm of MgCO3

Load: 2 tons Storage: 5 months

(figure 8 A) (figure 8 B)

Evaluation:

5 2

Table 3.3:

ABC according to the current state of the art, 8000 ppm of MgCO3

mixed crystals of ABC and 2 ppm of pectin, 8000 ppm of MgCO3

Load: 2 tons Storage: 6 months

(figure 9 A) (figure 9 B)

Evaluation:

4 one

Figure 7: While the ABC according to the current state of the art is very agglomerated, and even after moving the powder, large lumps remain, the mixed crystals according to the invention with pectin are very sliding and totally free of lumps.

Figure 8: While ABC according to the current state of the art is very agglomerated, and even after opening the bags, large and solid lumps remain, the mixed crystals according to the invention with pectin are very sliding. The smaller lumps disappear after moving the merchandise.

Figure 9: While ABC according to the current state of the art is very agglomerated, mixed crystals with pectins are very sliding and do not have lump formation.

15 4. Post-storage shift compared to EP 1 161 872

A layer of approx. 5 mm thick mixed ABC crystals with 25 ppm and 1000 ppm Tylose with approx. 6 cm in diameter for 10 minutes under a weight of 13.75 kg (approx. 500 g / cm2 pressure). The paper is then lifted and the compressed product is transferred to another paper and the degree of agglomeration is evaluated with the scale of example 3.

twenty

Table 4:

ABC with 1000 ppm of Tylose (comparison example in analogy with EP 1 161 872)

ABC with 25 ppm of Tylose

10 minutes at 500 g / cm2 pressure

(figure 10 A) (figure 10 B)

Outcome:

3 one

Note: The indication "ppm" in the examples is ppm by weight.

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

Claims (13)

1. Mixed crystals containing a) leavening agents b) 0.1 to 5000 ppm by weight of crystallization aids, in relation to the total amount of the leavening agent, in the form of at least one polymer, where using hydrophilic cellulose derivatives as crystallization aids is reduced its quantity at less than 100 ppm by weight, in relation to the total amount of the leavening agent.

2.

Mixed crystals according to claim 1, wherein the crystallization aid is at least one hydrophilic polymer that influences crystallization.

3.

Mixed crystals according to claim 1 or 2, wherein the crystallization aid is at least one polymer based on (hetero) polysaccharides and / or contains (poly) peptides.

Four.

Mixed crystals according to claims 1 to 3, wherein component b) contains 0.5 to 2000 ppm by weight of crystallization aids, in the form of at least one polymer, wherein when using hydrophilic cellulose derivatives as Crystallization aids are reduced in quantity to less than 80 ppm by weight.

5.

Mixed crystals according to claims 1 to 4, wherein component b) contains 1 to 100 ppm by weight of crystallization aids, in the form of at least one polymer, wherein when using hydrophilic cellulose derivatives as adjuvants of Crystallization reduces its amount to 1 to 50 ppm by weight.

6.

Mixed crystals according to claims 1 to 5, wherein as component b) polyacrylic acid or its salts with ammonium, sodium or potassium, polymethacrylic acid or its salts with ammonium, sodium or potassium, acrylic acid or its salts with ammonium are used, sodium or potassium, copolymer of methacrylic acid or its ammonium, sodium or potassium salts, copolymer of acrylic acid and maleic acid or its salts with ammonium, sodium or potassium, polyasparaginic acid or its salts, polyimines, polyvinylamines and copolymers with polyvinyl alcohol and / or poly-dimethyl-amyl ammonium chloride, polyethylene glycols, polypropylene glycols, random and block copolymers based on ethylene oxide with alkylene oxides methyl, ethyl, propyl, carboxymethyl, hydroxyethyl, hydroxypropyl, methylhydroxidethyl, methylhydroxypropyl, methylhydroxypropyl, methyl ethylhydroxidethyl, carboxymethylhydroxyethyl and / or benzylcellulose, alginic acid (E 400), sodium alginate (E 401), potassium alginate (E 402), a alginate monium (E 403), calcium alginate (E 404), propylene glycol alginate (E 405), agar-agar (E 406), carrageenan (E 407), processed Eucheuma algae (E 407a), locust bean seed meal ( E 410), guar seed meal (E 412), traganto (E 413), gum arabic (E414), xanthan (E 415), karaya (E 416), tara seed meal (E 417), gelano ( E 418), komjac / konjac rubber glucomannan (E 425), soy bean polysaccharide (E426), amidated pectin / pectin (E 440), microcrystalline cellulose / cellulose powder (E 460), methylcellulose (E 461), ethyl cellulose (E 462), hydroxypropyl cellulose (E 463), hydroxypropyl methylcellulose (E 464), ethyl methyl cellulose (E 465), sodium carboxymethyl cellulose / carboxymethyl cellulose (E 466), carboxymethyl cellulose carboxymethyl cellulose E (468) ), polydextrose (E 1200), polyvinylpyrrolidone (E 1201), polyvinylpolypyrrolidone (E 1202), polished (E 1204), oxidized starch (E 1404), monoalmidon phosphate (E 1410), dialmidon phosphate (E 1412), phosphate dialmidon phosphate (E 1413), acetylated dialmidon phosphate (E 1414), acetylated starch (E 1420), acetylated dialmidon adipate (E 1422), hydroxypropyl starch (E 1440), hydroxypropyldialmidon (E 1442), sodium octenyl succinate starch (E 1450), oxidized acetylated starch (E 1451).

7.

Mixed crystals according to claims 1 to 6, wherein component b) is selected from the group consisting of alginic acid (E 400), sodium alginate (E 401), potassium alginate (E 402), ammonium alginate ( E 403), calcium alginate (E 404), propylene glycol alginate (E 405), pectin (E 440), amidated pectin (E 440), carrageenan (E 407), gelane (E418), gum arabic (E414), karaya (E 416), traganto (E 413) and xanthan (E 415).

8.

Mixed crystals according to claim 1, wherein as component b) pectin and / or amidated pectin (E 440) is used.

9.

Mixed crystals according to claims 1 to 8, wherein, as a leavening agent, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, ammonium carbonate and / or ammonium hydrogen carbonate are used .

10.

Mixed crystals according to claims 1 to 8, wherein ammonium hydrogen carbonate is used as a leavening agent.

eleven.

Process for obtaining mixed crystals according to claims 1 to 10, characterized in that the crystallization aid is added before and / or during the crystallization step of the leavening agent.

12.

Process for obtaining bakery products, characterized in that the mixed crystals are used according to claims 1 to 10 as a modified leavening agent.

13.

Use of the mixed crystals according to claims 1 to 10 for obtaining bakery products, as a regulator of acidity in foods, in obtaining cosmetic products, in the synthesis and formulation of pharmaceutical products and as an expanding agent in procedures technicians